EP4174992A1 - Kathodenelektrokatalysator für metall-luft-batterien und herstellungsverfahren dafür - Google Patents

Kathodenelektrokatalysator für metall-luft-batterien und herstellungsverfahren dafür Download PDF

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EP4174992A1
EP4174992A1 EP21217717.4A EP21217717A EP4174992A1 EP 4174992 A1 EP4174992 A1 EP 4174992A1 EP 21217717 A EP21217717 A EP 21217717A EP 4174992 A1 EP4174992 A1 EP 4174992A1
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Prior art keywords
source
nitrogen
metal
precursor
solution
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French (fr)
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EP4174992B1 (de
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Chun-I Lee
Chun-Jern Pan
Yu-Ssu Kuo
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National Kaohsiung University of Science and Technology
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National Kaohsiung University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
    • C01B21/0622—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with iron, cobalt or nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8673—Electrically conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H01M4/8885—Sintering or firing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to an electrocatalyst for batteries and a production process thereof, and more particularly to a cathode electrocatalyst for metal-air batteries and a production process thereof.
  • CN 107195878 A discloses a process for producing a manganese (II) oxide/nitrogen-doped reduced graphene oxide composite electrode material.
  • the process includes the following steps.
  • Manganese(II) acetate tetrahydrate and urea are added into water, followed by evenly mixing through stirring, so as to obtain a solution.
  • Graphene oxide is added to the solution, followed by stirring and even dispersion through ultrasonication, so as to obtain a mixture.
  • the mixture is subjected to a hydrothermal reaction, which is performed at a temperature ranging from 120°C to 180°C for 4 to 12 hours.
  • the resultant product is subjected to filtration, washing, and drying, followed by heating under an inert atmosphere to a temperature ranging from 400°C to 600°C for a heating treatment to proceed for 2 to 5 hours. Therefore, the manganese (II) oxide/nitrogen-doped reduced graphene oxide composite electrode material is produced.
  • a first object of the present disclosure is to provide a process of producing a cathode electrocatalyst for metal-air batteries, which can alleviate at least one of the drawbacks of the prior art.
  • the process includes:
  • a second object of the present disclosure is to provide a cathode electrocatalyst for metal-air batteries, which can alleviate at least one of the drawbacks of the prior art, and which is produced by the aforesaid process.
  • an electrode material produced by a process including performing only a high-temperature hydrothermal reaction and then performing a heating treatment renders the service life of metal-air batteries unsatisfactory.
  • a heating treatment as disclosed in CN 107195878 A
  • the present disclosure provides a process of producing a cathode electrocatalyst for metal-air batteries, which includes:
  • the carbon source suspension may be prepared by dispersing the inorganic carbon source in a dispersion medium.
  • the inorganic carbon source may have a large surface area.
  • the inorganic carbon source has a surface area of at least 50 m 2 /g, so that the cathode electrocatalyst produced can enable a metal-air battery to have more satisfactory performance.
  • the inorganic carbon source may be selected from the group consisting of conductive carbon black, graphene, activated carbon, carbon fibers, carbon nanotubes, and combinations thereof.
  • the inorganic carbon source is conductive carbon black.
  • the dispersion medium is not particularly limited to any type of medium. Any liquid that can disperse the inorganic carbon source can be used as the dispersion medium.
  • the dispersion medium may be an alcohol.
  • the inorganic carbon source may be present in an amount ranging from 0.20 wt% to 0.45 wt% based on a total weight (i.e. 100 wt%) of the carbon source suspension, so that the dispersibility of the inorganic carbon source in the dispersion medium can be enhanced.
  • the inorganic carbon source is present in an amount ranging from 0.25 wt% to 0.40 wt% based on the total weight of the carbon source suspension.
  • the inorganic carbon source is present in an amount ranging from 0.30 wt% to 0.35 wt% based on the total weight of the carbon source suspension.
  • the metal source solution may be prepared by dissolving the soluble ionic compound in a first solvent to form an ionic compound solution, and by subsequently making a pH adjustment to the ionic compound solution.
  • the cathode electrocatalyst produced using the metal source solution having a pH value ranging from 6.5 to 10.5 can enable a metal-air battery to have satisfactory performance.
  • the metal source may be formed from any 3d transition metal.
  • the metal source may be selected from the group consisting of a cobalt source, a manganese source, an iron source, a nickel source, a chromium source, and combinations thereof.
  • the metal source is a cobalt source.
  • the soluble ionic compound may be selected from the group consisting of cobalt acetate, manganese acetate, iron acetate, nickel acetate, chromium acetate, and combinations thereof.
  • the first solvent is not particularly limited to any type of solvent. Any solvent that can dissolve the soluble ionic compound can be used as the first solvent.
  • the first solvent is water.
  • a molarity of the soluble ionic compound in the ionic compound solution may range from 0.2 mol/L to 0.6 mol/L. In certain embodiments, the molarity of the soluble ionic compound in the ionic compound solution ranges from 0.35 mol/L to 0.45 mol/L. Namely, a molarity of the metal source in the metal source solution may range from 0.2 mol/L to 0.6 mol/L, and in certain embodiments, the molarity of the metal source in the metal source solution ranges from 0.35 mol/L to 0.45 mol/L.
  • the nitrogen source solution may be prepared by dissolving the nitrogen-containing organic compound in a second solvent to form the nitrogen source.
  • any nitrogen-containing organic compound which has nitrogen atoms in the structure thereof, and a nitrogen source formed from which can be decomposed to release the nitrogen atoms, is suitable for the present disclosure.
  • the nitrogen-containing organic compound may be selected from the group consisting of urea, N-methylurea, N-ethylurea, acetamide, formamide, N-methylformamide, acrylamide, and combinations thereof.
  • the nitrogen-containing organic compound is urea.
  • the second solvent is not particularly limited to any type of solvent. Any solvent that can dissolve the nitrogen-containing organic compound can be used as the second solvent.
  • the second solvent is water.
  • a molarity of the nitrogen source in the nitrogen source solution may range from 0.8 mol/L to 6.7 mol/L. In certain embodiments, the molarity of the nitrogen source in the nitrogen source solution ranges from 1.67 mol/L to 4.5 mol/L.
  • a ratio of the molarity of the metal source in the metal source solution to that of the nitrogen source in the nitrogen source solution may range from 0.06 to 0.5, so that the cathode electrocatalyst produced can enable a metal-air battery to have more satisfactory performance.
  • the molarity ratio in decimal form ranges from 0.08 to 0.24. In other embodiments, the molarity ratio in decimal form ranges from 0.096 to 0.16.
  • the time required to conduct the low-temperature hydrothermal reaction indicates that the first precursor can be formed only by performing the low-temperature hydrothermal reaction at the temperature ranging from 70°C to 85°C for at least 20 hours. Therefore, the time required to conduct the low-temperature hydrothermal reaction can be more than 20 hours.
  • the time required to conduct the high-temperature hydrothermal reaction indicates that the second precursor can be formed only by performing the high-temperature hydrothermal reaction at the temperature exactly or substantially of 180°C for at least 12 hours. Therefore, the time required to conduct the high-temperature hydrothermal reaction can be more than 12 hours.
  • the temperature substantially of 180°C for conducting the high-temperature hydrothermal reaction may be 180°C ⁇ 2°C.
  • the protective atmosphere may be selected from the group consisting of a hydrogen gas, an argon gas, a nitrogen gas, an ammonia gas, and combinations thereof.
  • the protective atmosphere is a combination of a hydrogen gas and an argon gas.
  • the time for conducting the heating treatment is not particularly limited, and may be adjusted based on the temperature of the heating treatment.
  • the present disclosure also provides a cathode electrocatalyst for metal-air batteries, which is produced by the aforesaid production process.
  • Such cathode electrocatalyst is particularly suitable for making a metal-air rechargeable battery, and can enable the metal-air rechargeable battery to have not only satisfacotry performance but also a longer service life.
  • the cathode electrocatalyst may include a Co 4 N crystal phase, and may have an X-ray diffractogram obtainable through X-ray diffraction analysis.
  • the X-ray diffractogram may have a major peak exactly or substantially at 44.5° that represents the Co 4 N crystal phase.
  • conductive carbon black (Manufacturer: Cabot Corporation; Catalog No.: VXC-72R) was added into 8 mL of an alcohol, followed by conducting ultrasonic vibration for 10 minutes so that the conductive carbon black was evenly dispersed in the alcohol to obtain a carbon source suspension. Based on the total weight (i.e. 100 wt%) of the carbon source suspension, the amount of the conductive carbon black was 0.32 wt%.
  • Cobalt acetate was dissolved in deionized water to prepare an ionic compound solution containing cobalt acetate at a molarity of 0.4 mol/L.
  • a metal source solution having a pH value of 8.69 and containing a cobalt source at a molarity of 0.4 mol/L was prepared.
  • 2.0 g of urea was dissolved in 10 mL of deionized water to prepare a nitrogen source solution containing a nitrogen source at a molarity of 3.33 mol/L. Specifically, the nitrogen source was formed from urea.
  • the carbon source suspension and the metal source suspension were evenly mixed in a glass bottle, followed by sealing the glass bottle.
  • the glass bottle was placed in a silicone oil bath of 80°C and continuously heated for 20 hours for a low-temperature hydrothermal reaction to proceed, so that a first precursor-containing product was formed.
  • the cobalt source from the metal source solution was doped on the surface of the conductive carbon black from the carbon source suspension to form the first precursor in the first precursor-containing product.
  • the nitrogen source solution and the first precursor-containing product were mixed, followed by ultrasonic vibration for 30 minutes.
  • the resultant mixture was placed in a hydrothermal reactor.
  • the hydrothermal reactor was placed in an industrial oven and continuously heated at 180°C for 12 hours for a high-temperature hydrothermal reaction to proceed, so as to form a second precursor-containing product.
  • the nitrogen source from the nitrogen source solution was decomposed to form nitrogen atoms, which were further bonded to the cobalt source of the first precursor to form the second precursor of the second precursor-containing product.
  • the hydrothermal reactor was allowed to cool down, and the second precursor-containing product in the form of black powder was taken out from the hydrothermal reactor.
  • the second precursor-containing product and an anhydrous alcohol were mixed, followed by conducting a centrifugation process (at 4200 rpm for 5 minutes) twice.
  • the pellet thus obtained was placed in an oven having a temperature of 70°C for drying. Therefore, the second precursor in powder form was isolated.
  • the second precursor was subjected to a heating treatment at 400°C for 1 hour under a mixed atmosphere composed of a hydrogen gas (20%) and an argon gas (80%).
  • a mixed atmosphere composed of a hydrogen gas (20%) and an argon gas (80%).
  • the cathode electrocatalysts of Examples 2 to 5 were produced generally according to the procedure for producing that of Example 1, except that the amount of urea was modified for producing Examples 2 to 4, and that N-methylurea was used instead of urea for producing Example 5. The differences in detail are described as follows.
  • 0.5 g of urea was used to prepare a nitrogen source solution containing a nitrogen source at a molarity of 0.83 mol/L.
  • 1.0 g of urea was used to prepare a nitrogen source solution containing a nitrogen source at a molarity of 1.67 mol/L.
  • Example 4 For producing Example 4, 3.0 g of urea was used to prepare a nitrogen source solution containing a nitrogen source at a molarity of 5 mol/L.
  • Example 5 2.0 g of N-methylurea was used to prepare a nitrogen source solution containing a nitrogen source at a molarity of 2.7 mol/L.
  • the carbon source suspension, the metal source solution, and the nitrogen source solution for producing Comparative Example 1 were prepared according to the procedures for preparing those for producing Example 1.
  • the carbon source suspension, the metal source solution, and the nitrogen source solution were mixed under vibration for 30 minutes.
  • the resultant mixture was placed in a hydrothermal reactor.
  • the hydrothermal reactor was placed in an industrial oven and continuously heated at 180°C for 12 hours for a high-temperature hydrothermal reaction to proceed, so as to form a precursor-containing crude product.
  • the nitrogen source from the nitrogen source solution was decomposed to form nitrogen atoms, and the nitrogen atoms and the cobalt source from the metal source solution were together doped on the surface of the conductive carbon black from the carbon source suspension to form the precursor of the precursor-containing crude product.
  • the hydrothermal reactor was allowed to cool down, and the precursor-containing crude product in the form of black powder was taken out from the hydrothermal reactor.
  • the precursor-containing crude product and an anhydrous alcohol were mixed, followed by conducting a centrifugation process (at 4200 rpm for 5 minutes) twice.
  • the pellet thus obtained was placed in an oven having a temperature of 70°C for drying. Therefore, the precursor in powder form was isolated.
  • the precursor was subjected to a heating treatment at 400°C for 1 hour under a mixed atmosphere composed of a hydrogen gas (20%) and an argon gas (80%).
  • a mixed atmosphere composed of a hydrogen gas (20%) and an argon gas (80%).
  • the cathode electrocatalysts of Examples 1 and 5 and Comparative Example 1 were subjected to XRD analysis using an X-ray diffractometer (Bruker, D8 Advance). The X-ray diffractograms thus obtained are shown in FIG. 1 .
  • the cathode electrocatalyst thus produced has a Co 4 N crystal phase which can prolong the service life of a metal-air battery.
  • the cathode electrocatalysts of Example 1 and Comparative Example 1 had a Co 4 N crystal phase.
  • FWHM full width at half maximum intensity
  • Example 1 35 mg of the cathode electrocatalyst of Example 1, 20 ⁇ L of 20% PTFE (polytetrafluoroethylene) serving as an adhesive, and a tiny amount of an alcohol were evenly mixed to prepare a catalyst slurry.
  • the catalyst slurry was evenly coated on a surface of nickel foam having an area of 1 cm 2 .
  • the coated nickel foam was immersed in 20% PTFE, such that the catalyst slurry tightly adhered to the surface of the nickel foam.
  • NiFe layered double hydroxide (LDH) was evenly coated on the surface of the nickel foam having the catalyst slurry so as to prepare an air electrode.
  • LDH NiFe layered double hydroxide
  • a pure zinc metal electrode, an electrolyte (composed of a 6 M potassium hydroxide aqueous solution and a 0.2 M zinc acetate aqueous solution), and the air electrode were assembled to make a zinc-air rechargeable battery (also referred to as zinc-air secondary battery).
  • the zinc-air rechargeable battery was subjected to charge/discharge cycle testing for evaluating the performance thereof using a high-performance battery testing system (Neware, CT4008) under a respective one of the following three test conditions:
  • the cathode electrocatalysts of Examples 2 to 5 and Comparative Example 1 were used to make corresponding zinc-air rechargeable batteries according to the aforesaid procedure for making the zinc-air rechargeable battery employing the cathode electrocatalyst of Example 1.
  • the zinc-air rechargeable batteries respectively employing the cathode electrocatalysts of Examples 2 to 5 and Comparative Example 1 were subjected to charge/discharge cycle testing for evaluating the performance thereof using the aforesaid high-performance battery testing system under the test condition (1) described above.
  • the theoretical value of the voltage upon the oxygen reduction reaction (ORR) of a zinc-air rechargeable battery is 1.23 V. Therefore, when the actual value of the voltage upon the ORR of the zinc-air rechargeable battery is closer to 1.23 V, the zinc-air rechargeable battery has better performance.
  • the zinc-air rechargeable battery has a longer time period of stable charging and discharging, the zinc-air rechargeable battery has a longer service life. After the time period of stable charging and discharging, the voltage upon the discharging of the zinc-air rechargeable battery gradually decreases with increase in the number of charge/discharge cycles, gradually weakening the performance of the zinc-air rechargeable battery.
  • the voltage upon the ORR of the zinc-air rechargeable battery employing the cathode electrocatalyst of Example 1 was closer to the theoretical value (i.e. 1.23 V), had a longer time period of stable charging and discharging, and took a longer time to reach voltage reduction to 1.1 V upon discharging (also see FIG. 2 ).
  • the cathode electrocatalyst of Example 1 enabled the zinc-air rechargeable battery employing the same to have better performance and a longer service life.
  • the cathode electrocatalyst of the present disclosure which is produced by first conducting a low-temperature hydrothermal reaction and then conducting a high-temperature hydrothermal reaction, can enable a zinc-air rechargeable battery to have better performance and a longer service life.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
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EP21217717.4A 2021-10-26 2021-12-24 Kathodenelektrokatalysator für metall-luft-batterien und herstellungsverfahren dafür Active EP4174992B1 (de)

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